U.S. patent application number 14/419889 was filed with the patent office on 2015-07-23 for resin composition for laser direct structuring, resin molded article, and method for manufacturing molded resin article with plated layer.
This patent application is currently assigned to MITSUBISHI ENGINEERING-PLASTICS CORPORATION. The applicant listed for this patent is MITSUBISHI ENGINEERING-PLASTICS CORPORATION. Invention is credited to Hiroyoshi Maruyama, Atsushi Motegi.
Application Number | 20150203680 14/419889 |
Document ID | / |
Family ID | 49293810 |
Filed Date | 2015-07-23 |
United States Patent
Application |
20150203680 |
Kind Code |
A1 |
Motegi; Atsushi ; et
al. |
July 23, 2015 |
RESIN COMPOSITION FOR LASER DIRECT STRUCTURING, RESIN MOLDED
ARTICLE, AND METHOD FOR MANUFACTURING MOLDED RESIN ARTICLE WITH
PLATED LAYER
Abstract
Provided is a resin composition capable of achieving a higher
plating property. The resin composition comprises, relative to 100
parts by weight of a resin component comprising 30 to 100% by
weight of a polycarbonate resin and 70% by weight or less of a
styrene-based resin, 10 to 100 parts by weight of a glass fiber
having an average fiber length of 200 .mu.m or less and 2 to 20
parts by weight of a laser direct structuring additive.
Inventors: |
Motegi; Atsushi;
(Hiratsuka-shi, JP) ; Maruyama; Hiroyoshi;
(Hiratsuka-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MITSUBISHI ENGINEERING-PLASTICS CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
MITSUBISHI ENGINEERING-PLASTICS
CORPORATION
Tokyo
JP
|
Family ID: |
49293810 |
Appl. No.: |
14/419889 |
Filed: |
September 12, 2013 |
PCT Filed: |
September 12, 2013 |
PCT NO: |
PCT/JP2013/075387 |
371 Date: |
February 5, 2015 |
Current U.S.
Class: |
428/300.7 ;
427/123; 524/120; 524/140; 524/151; 524/409 |
Current CPC
Class: |
C08L 69/00 20130101;
C08L 2205/06 20130101; C08L 2207/53 20130101; C08L 69/00 20130101;
Y10T 428/24995 20150401; C08L 55/02 20130101; C08L 2205/035
20130101; C08L 2205/03 20130101; C08L 55/02 20130101; C08K 3/22
20130101; C08K 7/14 20130101; C08K 9/02 20130101; C08L 55/02
20130101; C08K 7/14 20130101; C08K 7/14 20130101; C08K 9/02
20130101; C08L 2203/20 20130101; C08L 69/00 20130101; C23C 22/00
20130101; C08K 3/22 20130101 |
International
Class: |
C08L 69/00 20060101
C08L069/00; C23C 22/00 20060101 C23C022/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 14, 2012 |
JP |
2012-203364 |
Claims
1-12. (canceled)
13. A resin composition for laser direct structuring, comprises,
relative to 100 parts by weight of a resin component comprising 30
to 100% by weight of a polycarbonate resin and 70% by weight or
less of a styrene-based resin, 10 to 100 parts by weight of a glass
fiber having an average fiber length of 200 .mu.m or less and 2 to
20 parts by weight of a laser direct structuring additive, wherein
the laser direct structuring additive is (1) a metal oxide
comprising, as a metal component, 90% by weight or more of tin and
2 to 7% by weight of antimony, and further comprising 0.0005% or
more by weight of lead and/or copper, or (2) a metal oxide particle
comprising titanium oxide coated with a composition comprising tin
as a main component and antimony.
14. The resin composition for laser direct structuring according to
claim 13, wherein the resin component comprises a styrene-based
resin in an amount of 10% by weight or more as a resin
component.
15. The resin composition for laser direct structuring according to
claim 13, further comprising at least one kind of an elastomer and
a phosphorus-based stabilizer.
16. The resin composition for laser direct structuring according to
claim 14, further comprising at least one kind of an elastomer and
a phosphorus-based stabilizer.
17. The resin composition for laser direct structuring according to
claim 13, which comprises the resin component in an amount of 60%
by weight or more of the total of the resin composition for laser
direct structuring.
18. The resin composition for laser direct structuring according to
claim 14, which comprises the resin component in an amount of 60%
by weight or more of the total of the resin composition for laser
direct structuring.
19. The resin composition for laser direct structuring according to
claim 15, which comprises the resin component in an amount of 60%
by weight or more of the total of the resin composition for laser
direct structuring.
20. The resin composition for laser direct structuring according to
claim 13, wherein an amount of a resin other than the polycarbonate
resin and styrene-based resin in the whole resin component is 5% by
weight or less.
21. The resin composition for laser direct structuring according to
claim 14, wherein an amount of a resin other than the polycarbonate
resin and styrene-based resin in the whole resin component is 5% by
weight or less.
22. The resin composition for laser direct structuring according to
claim 13, wherein the glass fiber is a milled fiber.
23. The resin composition for laser direct structuring according to
claim 13, wherein the glass fiber is coated with a sizing agent;
and the resin composition for laser direct structuring comprises
the sizing agent in an amount of 0.1 to 5.0% by weight of the glass
fiber.
24. The resin composition for laser direct structuring according to
claim 13, further comprising at least one kind selected from
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,
mono- and/or di-stearic acid phosphate, cyclic neopentanetetrayl
bis(octadecyl phosphite), and
tris(2,4-di-tert-butylphenyl)phosphite.
25. The resin composition for laser direct structuring according to
claim 13, further comprising a white pigment.
26. A resin-molded article obtained by molding the laser direct
structuring composition according to claim 13.
27. The resin-molded article according to claim 26, further
comprising a plated layer on a surface of the article.
28. The resin-molded article according to claim 27, wherein the
plated layer has a performance as an antenna.
29. The resin-molded article according to claim 26, which is a
mobile electronic device part.
30. A method for manufacturing a resin-molded article with a plated
layer, comprising irradiating the surface of a resin-molded
article, obtained by molding the thermoplastic resin composition
according to claim 13, with a laser, and then applying a metal to
form the plated layer.
31. The method for manufacturing a resin-molded article with a
plated layer according to claim 30, wherein the plated layer is
copper plated layer.
32. A method for manufacturing a mobile electronic device part
having an antenna, comprising the method for manufacturing a
resin-molded article with a plated layer according to claim 30.
Description
TECHNICAL FIELD
[0001] The present invention relates to a resin composition for
laser direct structuring (hereinafter may be simply referred to as
"resin composition"). Furthermore, the present invention relates to
a resin molded article produced by molding the resin composition,
and a method for manufacturing a resin molded article with a plated
layer in which the plated layer is formed, on the surface of the
resin molded article.
BACKGROUND ART
[0002] Recently, along with the development of cellular phones
including smart phone, various methods for manufacturing an antenna
inside the cellular phone have been studied. Particularly, a method
for manufacturing the antenna which can be three-dimensionally
designed inside the cellular phones is required. As one of the
techniques for forming the three-dimensional antenna, attention to
laser direct structuring (hereinafter may be referred to as "LDS")
technique has been paid. The LDS technique is a technique, for
example, where the irradiation of a surface of a resin molded
article containing an LDS additive with a laser activates only the
laser-irradiated portion, and then application of a metal to the
activated portion causes a plated layer to form. The feature of
this technique is to be capable of manufacturing a metallic
structure such as an antenna directly on a surface of resin
substrate without using adhesives or the like. Such LDS techniques
are disclosed, for example, in WO2011/095632 A, WO2011/076729 A,
and WO2011/076730 A.
SUMMARY OF INVENTION
Technical Problem
[0003] Here, along with the advancement of the LDS technique, there
is required a resin composition capable of achieving a higher
plating property. An object of the present invention is to solve
the problems of the conventional technique, and is to provide a
resin composition capable of achieving a higher plating
property.
Solution to Problem
[0004] Under such circumstances, as a result of intensive studies
by the present inventors, it has been found that, although blending
of a glass fiber is effective for enhancing mechanical properties,
when a fiber length of the glass fiber is long, a surface area of
the glass fiber becomes relatively smaller, which deteriorates
plating property. In addition, it has been found that, by
shortening of an average fiber length of the glass fiber, a resin
composition for LDS having an excellent plating property can be
provided, and then the present invention has been completed.
[0005] Specifically, the above-mentioned problems have been solved
by the means <1>, preferably by <2> to <12>
mentioned below.
<1> A resin composition for laser direct structuring,
comprises, relative to 100 parts by weight of a resin component
comprising 30 to 100% by weight of a polycarbonate resin and 70% by
weight or less of a styrene-based resin, 10 to 100 parts by weight
of a glass fiber having an average fiber length of 200 .mu.m or
less and 2 to 20 parts by weight of a laser direct structuring
additive. <2> The resin composition for laser direct
structuring according to <1>, wherein the laser direct
structuring additive comprises a metal oxide comprising tin and
antimony. <3> The resin composition for laser direct
structuring according to <1> or <2>, wherein the laser
direct structuring additive is (1) a metal oxide comprises, as a
metal component, 90% by weight or more of tin and 2 to 7% by weight
of antimony, and further comprising 0.0005% by weight of lead
and/or copper, or comprises (2) a metal oxide particle comprising
titanium oxide coated with a composition comprising tin as a main
component and antimony. <4> The resin composition for laser
direct structuring according to any one of <1> to <3>,
comprising styrene resin in an amount of 10% by weight or more as a
resin component. <5> The resin composition for laser direct
structuring according to any one of <1> to <4>, further
comprising an elastomer and/or a phosphorus-based stabilizer.
<6> A resin-molded article obtained by molding the laser
direct structuring composition according to any one of <1> to
<5>. <7> The resin-molded article according to
<6>, further comprising a plated layer on a surface of the
article. <8> The resin-molded article according to <6>
or <7>, which is a mobile electronic device part. <9>
The resin-molded article according to <7> or <8>,
wherein the plated layer has a performance as an antenna.
<10> A method for manufacturing a resin-molded article with a
plated layer, comprising irradiating the surface of a resin-molded
article, obtained by molding the thermoplastic resin composition
according to any one of <1> to <5>, with a laser, and
then applying a metal to form the plated layer. <11> The
method for manufacturing a resin-molded article with a plated layer
according to <10>, wherein the plating is copper plating.
<12> A method for manufacturing a mobile electronic device
part having an antenna, comprising the method for manufacturing a
resin-molded article with a plated layer according to <10> or
<11>.
Effects of the Invention
[0006] According to the present invention, it is possible to
provide a resin composition having an excellent plating
property.
BRIEF DESCRIPTION OF DRAWINGS
[0007] FIG. 1 is a schematic view showing a process of providing a
plated layer on a surface of resin molded article. In FIG. 1,
numeral 1 designates a resin molded article, 2 designates a laser,
3 designates a portion where irradiation with the laser is
performed, 4 designates a plating solution, 5 designates a plated
layer, respectively.
DESCRIPTION OF EMBODIMENTS
[0008] Hereinafter, the content of the present invention will be
specifically explained. Meanwhile, in the present Description, the
expression "to" is used to mean that the former numerical value and
the latter numerical value are included as an upper limit value and
a lower limit value, respectively.
[0009] The resin composition of the present invention comprises,
relative to 100 parts by weight of a resin component comprising 30
to 100% by weight of a polycarbonate resin and 70% by weight or
less of a styrene-based resin, 10 to 100 parts by weight of a glass
fiber having an average fiber length of 200 .mu.m or less and 2 to
20 parts by weight of a laser direct structuring additive.
According to this formulation, a higher plating property can be
achieved. Furthermore, there can be provided a resin composition
having excellent mechanical properties, low dielectric constant,
excellent hue, and being hard to be decomposed.
[0010] Hereinafter, the resin composition according to the present
invention will be explained in detail.
<Polycarbonate Resin>
[0011] The polycarbonate resin used in the present invention is not
particularly limited, and there can be used any of an aromatic
polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic
polycarbonate. Among them, the aromatic polycarbonate is
preferable, and more preferable is a thermoplastic aromatic
polycarbonate polymer or copolymer obtained by causing an aromatic
dihydroxy compound to react with phosgene or a diester of carbonic
acid.
[0012] The aromatic dihydroxy compounds include
2,2-bis(4-hydroxyphenyl)propane (=bisphenol A),
tetramethylbisphenol A, bis(4-hydroxyphenyl)-P-diisopropylbenzene,
hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc., and
preferable is bisphenol A. Furthermore, in order to prepare a
composition having high incombustibility, there can be used a
compound in which one or more of a tetraalkylphosphonium sulfonate
is bonded to the above-mentioned aromatic dihydroxy compound, or a
polymer, oligomer or the like containing siloxane structure and
having phenolic OH groups at both ends.
[0013] Preferred polycarbonate resins used in the present invention
comprise a polycarbonate resin derived from
2,2-bis(4-hydroxyphenyl)propane; and a polycarbonate copolymer
derived from 2,2-bis(4-hydroxyphenyl)propane and other aromatic
dihydroxy compound.
[0014] A molecular weight of the polycarbonate resin is a
viscosity-average molecular weight converted from a viscosity of
solution at a temperature of 25.degree. C. when using methylene
chloride as a solvent, and is preferably 14,000 to 30,000, more
preferably 15,000 to 28,000, and further preferably 16,000 to
26,000. When the viscosity-average molecular weight is within the
above-mentioned range, mechanical strength is good and moldability
is also good, which is thus preferable.
[0015] Method for preparing the polycarbonate resin is not
particularly limited, and in the present invention, there can be
used polycarbonate resins manufactured by any methods such as
phosgene method (interfacial polymerization method) and melting
method (interesterification method). In addition, in the present
invention, there may be used a polycarbonate resin manufactured
through a process in which an amount of end OH groups is controlled
after undergoing manufacturing process by the general melting
method.
[0016] Moreover, the polycarbonate resin used in the present
invention may be not only a polycarbonate resin as a virgin
material, but also a polycarbonate resin recycled from used
products, so called a polycarbonate resin materially recycled.
[0017] As to other polycarbonate resins used in the present
invention, the description of, for example, paragraphs 0018 to 0066
of JP 2012-072338 A can be referred to, which is incorporated
hereto.
[0018] The resin composition of the present invention may comprise
only one kind of the polycarbonate resin, or may comprise two or
more kinds.
[0019] In the resin composition of the present invention, a
proportion of the polycarbonate resin in the whole resin components
is preferably 30 to 100% by weight, more preferably 45 to 75% by
weight, and further preferably 52 to 70% by weight.
<Styrene-Based Resin>
[0020] The resin composition of the present invention may comprise
a styrene-based resin other than the polycarbonate resin, as resin
components.
[0021] The styrene-based resin refers to at least one polymer
selected from the group consisting of a styrene-based polymer
comprising a styrene-based monomer; a copolymer of the
styrene-based monomer and the other copolymerizable vinyl monomer;
a polymer obtained by polymerizing styrene-based monomers, or by
copolymerizing styrene-based monomers and other polymerizable vinyl
monomers copolymerizable with the styrene-based monomer, in the
presence of a rubber-like polymer. Among them, it is preferable to
use the copolymer obtained by copolymerizing the styrene-based
monomers or the copolymer of the styrene-based monomer and the
other copolymerizable vinyl monomer, in the presence of a
rubber-like polymer.
[0022] Specific examples of the styrene-based monomers include
styrene, a styrene derivative such as .alpha.-methylstyrene,
p-methylstyrene, divinylbenzene, ethylvinylbenzene,
dimethylstyrene, p-t-butylstyrene, bromostyrene, or dibromostyrene,
and among them, styrene is preferable. Meanwhile, these may be used
alone or in the mixture of two or more of them.
[0023] Examples of the vinyl-based monomer copolymerizable with the
above-mentioned styrene-based monomer include a vinyl cyan compound
such as acrylonitrile or methacrylonitrile, an alkyl ester of
acrylic acid such as methyl acrylate, ethyl acrylate, propyl
acrylate, butyl acrylate, amyl acrylate, hexyl acrylate,
2-ethylhexyl acrylate, octyl acrylate or cyclohexyl acrylate, an
alkyl ester of methacrylic acid such as methyl methacrylate, ethyl
methacrylate, propyl methacrylate, butyl methacrylate, amyl
methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl
methacrylate or cyclohexyl methacrylate, an aryl ester of acrylic
acid such as phenyl acrylate or benzyl acrylate, an aryl ester of
methacrylic acid such as phenyl methacrylate or benzyl
methacrylate, an epoxy-containing acrylic ester or metacrylic ester
such as glycidyl acrylate or glycidyl methacrylate, a
maleimide-based monomer such as maleimide, N,N-methyl maleimide or
N-phenyl maleimide, an .alpha.,.beta.-unsaturated carboxylic acid
or acid anhydride thereof such as acrylic acid, methacrylic acid,
maleic acid, maleic acid anhydride, fumaric acid or itaconic acid,
and the like.
[0024] In addition, examples of the rubber-like polymer
copolymerizable with the styrene-based monomer include
polybutadiene, polyisoprene, styrene-butadiene random copolymer and
block copolymer, acrylonitrile-butadiene random copolymer and block
copolymer, acrylonitrile-butadiene copolymer, a copolymer of
butadiene and an alkyl ester of acrylic acid or an alkyl ester of
methacrylic acid, polybutadiene-polyisoprene diene-based copolymer,
a copolymer of ethylene and an .alpha.-olefin such as
ethylene-isoprene random copolymer and block copolymer or
ethylene-butene random copolymer and block copolymer, a copolymer
of ethylene and an .alpha.,.beta.-unsaturated carboxylic acid ester
such as ethylene-methacrylate copolymer or ethylene-butyl acrylate
copolymer, ethylene-vinyl acetate copolymer, an
ethylene-propylene-unconjugated diene terpolymer such as
ethylene-propylene-hexadiene copolymer, acryl rubber, a composite
rubber composed of polyorganosiloxane rubber and a polyalkyl
acrylate or methacrylate rubber, and the like.
[0025] Examples of such styrene-based resins include, for example,
polystyrene resin, high impact polystyrene resin (HIPS),
acrylonitrile-styrene copolymer (AS resin),
acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl
methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS
resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin),
acrylonitrile-ethylenepropylene based rubber-styrene copolymer (AES
resin), styrene-methyl methacrylate copolymer (MS resin),
styrene-maleic acid anhydride copolymer and the like.
[0026] Among them, preferable is acrylonitrile-styrene copolymer
(AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin),
acrylonitrile-styrene-acrylic rubber copolymer (ASA resin) or
acrylonitrile-ethylenepropylene based rubber-styrene copolymer (AES
resin), more preferable is acrylonitrile-butadiene-styrene
copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber
copolymer (ASA resin) or acrylonitrile-ethylenepropylene based
rubber-styrene copolymer (AES resin), particularly preferable is
acrylonitrile-butadiene-styrene copolymer (ABS resin).
[0027] The above-mentioned styrene-based resin is prepared by a
method such as emulsion polymerization, solution polymerization,
mass polymerization, suspension polymerization or mass-suspension
polymerization, but in the present invention, in the case of
so-called styrene-based polymer, or the styrene-based random
copolymer of block copolymer, a styrene-based resin prepared by
mass polymerization, suspension polymerization or mass-suspension
polymerization is suitable, and in the case of the styrene-based
graft copolymer, a styrene-based resin prepared by mass
polymerization, mass-suspension polymerization or emulsion
polymerization is suitable.
[0028] In the present invention, the
acrylonitrile-butadiene-styrene copolymer (ABS resin) particularly
favorably used is a mixture of a thermoplastic graft copolymer
prepared by grafting acrylonitirile and styrene to a butadiene
rubber component, and a copolymer of acrylonitirile and styrene.
The butadiene rubber component is preferably 5 to 40% by weight in
100% by weight of the ABS resin component, more preferably 10 to
35% by weight, and particularly preferably 13 to 25% by weight. In
addition, the rubber particle size is preferably 0.1 to 5 .mu.m,
more preferably 0.2 to 3 .mu.m, further preferably 0.3 to 1.5
.mu.m, and particularly preferably 0.4 to 0.9 .mu.m. The
distribution of the rubber particle size may be any of a uniform
distribution or be a plurality of distributions having two or more
peaks.
[0029] The resin composition of the present invention may comprise
only one kind of the styrene-based resin, or may comprise two or
more kinds.
[0030] In the resin composition of the present invention, a
proportion of the styrene-based resin in the whole resin components
is preferably 70% by weight or less, more preferably 55% by weight
or less, and further preferably 45% by weight or less. In addition,
a proportion of the styrene-based resin in the whole resin
components is preferably 10% by weight or more, and more preferably
30% by weight or more.
[0031] Furthermore, the resin composition of the present invention
may comprise other resin component within a scope not departing the
gist of the present invention. However, the other resin is
preferably 5% by weight or less in the whole resin components.
[0032] In the resin composition of the present invention, the resin
components is preferably 60% by weight or more of the total of the
composition, more preferably 70% by weight or more.
<Glass Filler>
[0033] The resin composition of the present invention comprises a
glass fiber having an average fiber length of 200 .mu.m or less. By
adding such a glass fiber, the plating property of the composition
is improved.
[0034] The glass fiber refers to a material which has a perfect
circular or polygonal cross-sectional shape cut at right angles to
the longitudinal direction and has a fibrous appearance. The glass
filler is made up of glass composition such as A glass, C glass, E
glass, and S glass and particularly, the E glass (no alkaline
glass) is preferable because it does not have an adverse effect on
the polycarbonate resin.
[0035] The average fiber length of the glass fiber used in the
present invention is preferably 150 .mu.m or less, further
preferably 120 .mu.m or less. The upper limit is preferably 5 .mu.m
or more, more preferably 7 .mu.m or more, further more preferably
15 .mu.m or more. The average fiber diameter is preferably 5 to 15
.mu.m, more preferably 7 to 15 .mu.m, particularly preferably 9 to
15 .mu.m. When the average fiber diameter is less than 5 .mu.m,
there may be a case where a moldability of the polycarbonate resin
composition is impaired, and when the average fiber diameter
exceeds 15 .mu.m, there is a case where an appearance of the resin
molded article is impaired and reinforcing effect is not
sufficient. The glass fiber may be a monofilament or a plurality of
monofilament twisted threads. Meanwhile, in the present invention,
the average fiber diameter is a weight average fiber diameter.
[0036] The shape of the glass fibers may be any of "glass roving"
obtained by winding continuously a monofilament or a plurality of
monofilament twisted threads, "chopped strand" cut at a length of 1
to 10 mm, or "milled fiber" milled to powder having a length of
about 10 to 500 .mu.m. Such glass fibers can be commercially
manufactured by ASAHI FIBER GLASS Co., Ltd. as a trade name of
"Glasslon Chopped Strand" or "Glasslon Milled Fiber", and can be
easily obtained. The glass fibers of different shapes can also be
used together.
[0037] In addition, according to the present invention, a glass
fiber having an irregular cross-sectional shape is also preferable.
This irregular cross-sectional profile means that, when a longer
diameter and a shorter diameter of a cross section perpendicular to
a fiber length are assumed to be D2 and D1, respectively, a
flattening ratio represented by a ratio of longer diameter/shorter
diameter (D2/D1) is, for example, preferably 1.5 to 10, more
preferably 2.5 to 10, further preferably 2.5 to 8, and particularly
preferably 2.5 to 5. This flat glass fiber is referred to the
description of Paragraphs 0065 to 0072 of JP 2011-195820 A, which
are incorporated herein.
[0038] A blending amount of the glass filler in the resin
composition of the present invention is 10 to 100 parts by weight,
preferably 10 to 85 parts by weight, more preferably 20 to 70 parts
by weight, further preferably 30 to 65 parts by weight, and
particularly preferably 40 to 60 parts by weight relative to 100
parts by weight of the resin component. By blending the glass
filler, the mechanical strength can be enhanced and also plating
property tend to be enhanced.
[0039] The resin composition of the present invention may comprise
only one kind of the glass filler, or may comprise two or more
kinds. When comprising two or more of them, it is preferable that a
total amount is within the above-mentioned range.
<Sizing Agent>
[0040] The glass fiber to be blended with the resin composition of
the present invention is preferably coated with a sizing agent. A
kind of the sizing agent is not particularly limited. The sizing
agent may be used only one kind or may be used in combination of
two or more kinds.
[0041] Furthermore, as one example of the present invention, there
is exemplified an embodiment in which at least one sizing agent
selected from an epoxy-based sizing agent, an urethane-based sizing
agent, a polyolefin-based sizing agent, and a silicone-based sizing
agent, and more preferable sizing agent are polyolefin-based sizing
agent and silicone-based sizing agent. Such a sizing agent has a
poor adhesion property to the resin component comprising the
polycarbonate resin according to the present invention. Therefore,
in the case of the resin composition comprising such a glass fiber,
a clearance is formed between the glass fiber and the resin
component, and a plating solution enters the clearance, which makes
it possible to enhance the plating property.
[0042] The polyolefin resins to be used as the sizing agent include
polyethylene resin, polypropylene resin, a coating agent comprising
a polyolefin described in Japanese Patent No. 4880823, and the
like. Among them, from the viewpoint of adhesion property,
polyethylene is preferable. Examples of the silicone resins include
acrylsilane resin, a coating agent comprising a polyorganosiloxane
described in Japanese Patent No. 4880823, and the like. The
polyolefin resin and/or the silicone resin may be formed of a
single monomer or may be a copolymer formed of a plurality of
different monomers.
[0043] An amount of the sizing agent in the resin composition of
the present invention is preferably 0.1 to 5.0% by weight of the
glass fiber, more preferably 0.2 to 2.0% by weight.
<Laser Direct Structuring Additive>
[0044] The resin composition of the present invention comprises a
LDS additive.
[0045] The LDS additive used in the present invention refers to a
compound in which a plated layer can be formed when adding 4 parts
by weight of an additive to be considered as a LDS additive
relative to 100 parts by weight of polycarbonate resin (Iupilon
(registered trademark) S-3000F manufactured by Mitsubishi
Engineering Plastics Co., Ltd.), performing irradiation with YAG
laser having a wavelength of 1064 nm under output power of 10 W,
frequency of 80 kHz and rate of 3 m/s, and then subjecting the
laser-irradiated surface as metal, to a plating process in an
electroless plating bath of M-Copper85 manufactured by MacDermid
Co., Ltd. The LDS additive to be used in the present invention may
be a synthetic product or a commercially available product.
Furthermore, the commercially available product may be a product
being commercial product sold as a LDS additive, or may be a
material which is sold for other use as long as the requirements of
the LDS according to the present invention is satisfied.
[0046] Among them, the LDS additives preferably comprise tin and
antimony from the viewpoint of the improved plating property.
[0047] A particle size of the LDS additive is preferably 0.01 to 50
.mu.m, more preferably 0.05 to 30 .mu.m. With such a structure, the
uniformity of plated surface condition when applying plating tends
to be excellent.
[0048] Hereinafter, the preferred embodiments of the LDS additives
used in the present invention are explained. By employing the
embodiments, the effects of the present invention tend to be more
effective. However, it goes without saying that the present
invention is not limited to the embodiments.
[0049] The first embodiment of the LDS additive of the present
invention is a metal oxide comprising 90% by weight or more of tin,
2 to 7% by weight of antimony, and lead and/or copper in an amount
of 0.0005% by weight or more. By blending a small amount of lead
and/or copper, the plating property is improved.
[0050] The first embodiment of the LDS additive is specifically a
LDS additive comprising tin oxide doped with antimony or tin oxide
doped with antimony oxide which comprises at least any one of lead,
lead oxide, copper and copper oxide.
[0051] The LDS additive of the first embodiment preferably
comprises metal component comprising 90% by weight or more of tin,
more preferably 93 to 97% by weight of tin. The amount of antimony
in the metal component is preferably 3 to 7% by weight, more
preferably 3 to 5% by weight.
[0052] Among of the metal component in the LDS additive, the total
amount of lead and copper is preferably 0.0005% by weight or more,
more preferably 0.001% by weight or more, still more preferably
0.01% by weight or more. The upper limit is preferably 0.1% by
weight.
[0053] When the oxide in the LDS additive is tin oxide, the amount
of the tin oxide is preferably 90 to 97% by weight, more preferably
92 to 96% by weight. When the oxide in the LDS additive is antimony
oxide, the amount of the antimony oxide is preferably 2 to 7% by
weight, more preferably 3 to 6% by weight. When the oxide in the
LDS additive is lead oxide, the amount of the lead oxide is
preferably 0.01 to 0.1% by weight. When the oxide in the LDS
additive is copper oxide, the amount of the copper oxide is
preferably 0.001 to 0.01% by weight, more preferably 0.003 to
0.008% by weight.
[0054] The LDS additive used in the present invention may comprise
a small amount of other metals other than lead and/or copper.
Examples of the other metals include indium, iron, cobalt, nickel,
zinc, cadmium, silver, bismuth, arsenic, manganese, chromium,
magnesium, calcium, and the like. These metals may exist in the
form of oxide. The content of the metals is preferably 0.001% by
weight or less of the metal components contained in the LDS
additive.
[0055] The second embodiment of the LDS additive used in the
present invention is a LDS additive comprising a metal oxide
particle comprising titanium oxide which is coated with a
composition comprising tin as a main component and antimony
(hereinafter may be referred to as coating composition). By coating
the metal oxide particle with the coating composition, a plating
property can be enhanced.
[0056] The metal oxide particle comprises titanium oxide, and an
amount of titanium oxide is preferably 90% by weight or more, more
preferably 95% by weight or more, and further preferably 99% by
weight or more.
[0057] The metal oxide particle may comprise a metal other than
titanium oxide. Examples of the metals other than titanium oxide
include indium, iron, cobalt, nickel, zinc, cadmium, silver,
bismuth, arsenic, manganese, chromium, magnesium, calcium, and the
like. These metals may exist in the form of oxide. The content of
those metals is preferably 0.01% by weight or less.
[0058] The coating composition is a metal oxide composition
comprising tin as a main ingredient and antimony, and examples
thereof include tin oxide doped with antimony and tin oxide doped
with antimony oxide. The coating composition may be the LDS
additive shown in the above first embodiment.
[0059] The LDS additive may be coated with the coating composition
on a part of the surface of the metal oxide particle, or may be
coated with the coating composition on the whole of the
surface.
[0060] A weight ratio of the metal oxide particle and the coating
composition (metal oxide particle:coating composition) is
preferably 90:10 to 60:40, more preferably 85:15 to 75:25.
[0061] The third embodiment of the LDS additive is a LDS additive
comprising copper oxide. The LDS additive in the third embodiment
preferably comprises an oxide comprising copper and chrome, further
preferably comprises an oxide comprising only copper and chrome as
a metal component. The amount of copper in the LDS additive is
preferably 20 to 95% by weight.
[0062] A blending amount of the LDS additive in the resin
composition of the present invention is 2 to 20 parts by weight,
preferably 3 to 15 parts by weight, more preferably 5 to 12 parts
by weight relative to 100 parts by weight of the resin
component.
[0063] In addition, by blending a talc, a sufficient plating
property can be achieved even if a blending amount of the LDS
additive is adjusted to be a small amount (for example, 3 to 7
parts by weight relative to 100 parts by weight of the resin
component).
[0064] The resin composition of the present invention may comprise
only one kind of the LDS additive, or may comprise two or more
kinds. When comprising two or more of them, it is preferable that a
total amount is within the above-mentioned range.
<Talc>
[0065] The resin composition of the present invention may comprise
a talc. In the present invention, by blending the talc, plating
performance at the portion irradiated with laser tends to be
increased.
[0066] In addition, the talc used in the present invention is
preferable to be a talc surface-treated with at least one of a
compound selected from polyorganohydrogensiloxanes and
organopolysiloxanes. In this case, an adhesion amount of the
siloxane compound is preferably 0.1 to 5% by weight of the talc.
The siloxane compound will be explained specifically in the
following.
[0067] When the resin composition of the present invention contains
the talc, a blending amount of the talc is preferably 1 to 30 parts
by weight, and more preferably 2 to 10 parts by weight relative to
100 parts by weight of the resin component. When the talc is
surface-treated, it is preferable that a total amount of the
surface-treated talc is within the above-mentioned range.
<Elastomer>
[0068] It is also preferable that the resin composition of the
present invention comprises an elastomer. By blending the
elastomer, an impact resistance of the resin composition can be
enhanced.
[0069] The elastomer used in the present invention is preferably a
graft copolymer prepared by graft-copolymerizing a rubber component
with a copolymerizable monomer component. Preparation method of the
graft copolymer may be anyone of mass polymerization, solution
polymerization, suspension polymerization, emulsion polymerization,
and the like, and copolymerization system may be one-stage grafting
or multi-stage grafting.
[0070] The rubber component has a glass transition temperature of
usually 0.degree. C. or less, more preferably -20.degree. C. or
less, further preferably -30.degree. C. or less. Specific examples
of the rubber component include polybutadiene rubber, polyisoprene
rubber, a polyalkyl acrylate rubber such as polybutyl acrylate,
poly(2-ethylhexyl acrylate), or copolymer of butyl acrylate and
2-ethylhexyl acrylate, a silicone-based rubber such as
polyorganosiloxane rubber, butadiene-acryl composite rubber, IPN
(Interpenetrating Polymer Network) type composite rubber composed
of polyorganosiloxane rubber and polyalkyl acrylate rubber,
styrene-butadiene rubber, an ethylene-.alpha.-olefin-based rubber
such as ethylene-propylene rubber, ethylene-butene rubber or
ethylene-octene rubber, ethylene-acryl rubber, fluororubber, and
the like. These may be used alone or in combination of two or more
of them. Among them, from the viewpoint of mechanical properties
and surface appearance, preferable are polybutadiene rubber,
polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN type
composite rubber composed of polyorganosiloxane rubber and
polyalkyl acrylate rubber, styrene-butadiene rubber.
[0071] Specific examples of the monomer component
graft-copolymerizable with the rubber component include an aromatic
vinyl compound, a vinyl cyanide compound, an ester compound of
(meth)acrylic acid, a (meth)acrylic acid compound, an ester
compound of an epoxy-containing (meth)acrylic acid such as
glycidyl(meth)acrylate; a maleimide compound such as maleimide,
N-methylmaleimide, or N-phenylmaleimide; an
.alpha.,.beta.-unsaturated carboxylic acid compound such as maleic
acid, phthalic acid, or itaconic acid, and an acid anhydride
thereof (for example maleic acid anhydride, and the like), and the
like. These monomers may be used alone or in combination of two or
more of them. Among them, from the viewpoint of mechanical
properties and surface appearance, preferable are an aromatic vinyl
compound, a vinyl cyanide compound, an ester compound of
(meth)acrylic acid, a (meth)acrylic acid compound, and more
preferable is an ester compound of (meth)acrylic acid. Specific
examples of the ester compound of (meth)acrylic acid include
methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate,
cyclohexyl(meth)acrylate, octyl(meth)acrylate, and the like.
[0072] In view of impact resistance and surface appearance, the
graft copolymer which is copolymerized with the rubber component is
preferably a core/shell type graft copolymer. Among them,
particularly preferable is a core/shell type graft copolymer which
is composed of a core layer of at least one of the rubber component
selected from polybutadiene-containing rubber, polybutyl
acrylate-containing rubber, polyorganosiloxane rubber and IPN type
composite rubber composed of polyorganosiloxane rubber and
polyalkyl acrylate rubber, and a shell layer which is formed around
the core by copolymerizing a (meth)acrylic acid ester. In the
above-mentioned core/shell type graft copolymer, a content of the
rubber component is preferably 40% by mass or more, more preferably
60% by mass or more. A content of the (meth)acrylic acid is
preferably 10% by mass or more. In the present invention, the
core/shell type is not necessary to exactly distinguish the core
layer from the shell layer, and has a concept that includes
compounds obtainable by graft-polymerizing the rubber component
around the core portion.
[0073] Preferable examples of the core/shell type graft copolymer
include methyl methacrylate-butadiene-styrene copolymer (MBS),
methyl methacrylate-acrylonitrile-butadiene-styrene copolymer
(MABS), methyl methacrylate-butadiene copolymer (MB), methyl
methacrylate-acryl rubber copolymer (MA), methyl methacrylate-acryl
rubber-styrene copolymer (MAS), methyl methacrylate-acryl butadiene
rubber copolymer, methyl methacrylate-acryl butadiene
rubber-styrene copolymer, methyl methacrylate-(acryl silicone IPN
rubber) copolymer, and the like. These rubber-like polymers may be
used alone or in combination of two or more of them.
[0074] Examples of the elastomer include, for instance, "PARALOID
(registered trademark, hereinafter the same) EXL2602", "PARALOID
EXL2603", "PARALOID EXL2655", "PARALOID EXL2311", "PARALOID
EXL2313", "PARALOID EXL2315", "PARALOID KM330", "PARALOID KM336P",
"PARALOID KCZ201" manufactured by Rohm and Haas Japan Company,
"METABLEN (registered trademark, hereinafter the same) C-223A",
"METABLEN E-901", "METABLEN S-2001", "METABLEN SRK-200"
manufactured by MITSUBISHI RAYON Co., Ltd., KANEACE (registered
trademark, hereinafter the same) M-511, "KANEACE M-600", "KANEACE
M-400", "KANEACE M-580", "KANEACE M-711", "KANEACE MR-01"
manufactured by KANEKA CORPORATION, "UBESTA XPA" manufactured by
UBE INDUSTRIES LTD, and the like.
[0075] When the resin composition of the present invention contains
an elastomer, a blending amount of the elastomer is 1 to 20 parts
by weight, preferably 1 to 15 parts by weight, more preferably 3 to
10 parts by weight relative to 100 parts by weight of the resin
component.
[0076] The resin composition of the present invention may comprise
only one kind of the elastomer, or may comprise two or more kinds.
When comprising two or more of them, it is preferable that a total
amount is within the above-mentioned range.
<White Pigment>
[0077] The resin composition of the present invention may comprise
a white pigment. In the present invention, by adding the white
pigment, coloring of the resin-molded article can be achieved.
Examples of the white pigments include ZnS, ZnO, titanium oxide,
and preferable are zinc sulfide and titanium oxide.
[0078] The titanium oxide is preferably one which contains titanium
oxide in an amount of 80% by weight or more among commercially
available ones in view of whiteness and covering property. Examples
of the titanium oxide used in the present invention include
titanium monoxide (TiO), dititanium trioxide (Ti.sub.2O.sub.3),
titanium dioxide (TiO.sub.2), and the like, and any of them can be
used, preferable is titanium dioxide. As the titanium oxide, there
may be used one having the rutile type crystalline structure.
[0079] An average primary particle size of the white pigment is
preferably 1 .mu.m or less, more preferably within a range of from
0.001 to 0.5 .mu.m, further preferably within a range of from 0.002
to 0.1 .mu.m. By controlling the average particle size of the white
pigment within such a range and an amount thereof within the
following range, it is possible to obtain a resin composition which
produces a molded article having a high whiteness and high surface
reflectance.
[0080] When using an inorganic pigment as the white pigment, a
surface-treated pigment may be used. The white pigment used in the
present invention is preferably a white pigment which is
surface-treated with at least one of the siloxane compound. In the
case, an adhesion amount of the siloxane compound is preferably 0.1
to 5% by weight of the white pigment. As to the siloxane compound,
the explanation of the above-mentioned polyorganohydrogensiloxanes
and organopolysiloxanes can be referred to, and the preferred
ranges are also the same.
[0081] As a preferred embodiment of the present invention, there is
exemplified a formulation using a titanium oxide surface-treated
with at least one kind selected from polyorganohydrogensiloxanes
and organopolysiloxanes.
[0082] As the white pigment, commercially available pigments can be
used. Furthermore, it may be possible to use one obtained by
grinding appropriately a massive pigment or a pigment with large
average particle size, and classifying the pigment with a sieve or
the like, if necessary, so as to be within the above-mentioned
average particle size
[0083] When the resin composition of the present invention
comprises the white pigment, a blending amount of the white pigment
is preferably 0.1 to 10 parts by weight, more preferably 1 to 8
parts by weight, and further preferably 2 to 5 parts by weight
relative to 100 parts by weight of the resin component.
[0084] The polycarbonate resin composition of the present invention
may comprise only one kind of the white pigment, or may comprise
two or more kinds. When comprising two or more of them, it is
preferable that a total amount is within the above-mentioned
range.
<Phosphorus-Based Stabilizer>
[0085] The resin composition of the present invention preferably
comprises a phosphorus-based stabilizer.
[0086] As the phosphorus-based stabilizer, a phosphoric acid ester
and a phosphorous acid ester are preferable.
[0087] As the phosphoric acid ester, the compound represented by
the following general formula (3) is preferable.
General formula (3)
O.dbd.P(OH).sub.m(OR).sub.3-m (3)
in the general formula (3), R is an alkyl group or an aryl group,
and may be the same or different. m is an integer of 0 to 2.
[0088] R is preferably an alkyl group having 1 to 30 carbon atoms
or an aryl group having 6 to 30 carbon atoms, R is preferably an
alkyl group having 1 to 30 carbon atoms or an aryl group having 6
to 30 carbon atoms, and more preferable are an alkyl group having 2
to 25 carbon atoms, phenyl group, nonylphenyl group, stearylphenyl
group, 2,4-di-tert-butylpheny group, 2,4-di-tert-butylmethylphenyl
group, tolyl group.
[0089] Examples of the phosphoric acid esters include trimethyl
phosphate, triethyl phosphate, tributyl phosphate, trioctyl
phosphate, triphenyl phosphate, tricresyl phosphate,
tris(nonylphenyl)phosphate, 2-ethylphenyl diphenyl phosphate,
tetrakis(2,4-di-tert-butylphenyl)-4,4-diphenylenephosphonit e and
the like.
[0090] As the phosphorous acid ester, the compound represented by
the following general formula (4) is preferable.
General formula (4)
##STR00001##
[0091] in the general formula (4), R' is an alkyl group or an aryl
group, and each may be the same or different.
[0092] R' is preferably an alkyl group having 1 to 25 carbon atoms,
or an aryl group having 6 to 12 carbon atoms. When R' is an alkyl
group, an alkyl group having 1 to 30 carbon atoms is preferable,
and when R' is an aryl group, an aryl group having 6 to 30 carbon
atoms is preferable.
[0093] Examples of the phosphorous acid esters include a triester,
a diester, or a monoester of phosphorous acid such as triphenyl
phosphite, trisnonylphenyl phosphite,
tris(2,4-di-tert-butylphenyl)phosphite, trinonyl phosphite,
tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite,
distearylpentaerythritol diphosphite, tricyclohexyl phosphite,
monobutyldiphenyl phosphite, monooctyldiphenyl phosphite,
bis(2,4-di-tert-butylphenyl)pentaerythritol phosphite,
bis(2,6-di-tert-4-methylphenyl)pentaerythritol phosphite,
2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite and the
like.
[0094] When the resin composition of the present invention
comprises the phosphorus-based stabilizer, a blending amount of the
phosphorus-based stabilizer is 0.01 to 5 parts by weight, and more
preferably 0.02 to 2 parts by weight relative to 100 parts by
weight of the resin component.
[0095] The resin composition of the present invention may comprise
only one kind of the phosphorus-based stabilizer, or may comprise
two or more kinds. When comprising two or more of them, it is
preferable that a total amount is within the above-mentioned
range.
<Antioxidant>
[0096] The resin composition of the present invention may comprise
an antioxidant. The antioxidant is preferably a phenol-based
antioxidant, and includes more specifically,
2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3
,5'-di-t-butyl-4'-hydroxyphenyl) propionate,
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)
propionate]methane, tris(3,5-di-t-butyl-4-hydroxybenzyl)
isocyanurate, 4,4'-butylydenebis-(3-methyl-6-t-butylphenol),
triethylene glycol-bis[3-(3-t-butyl-hydroxy-5-methylphenyl)
propionate, and
3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimeth-
ylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, etc. Among them,
preferable is
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methan-
e.
[0097] When the resin composition of the present invention
comprises the antioxidant, a blending amount of the antioxidant is
0.01 to 5 parts by weight, and more preferably 0.05 to 3 parts by
weight relative to 100 parts by weight of the resin component.
[0098] The resin composition of the present invention may comprise
only one kind of the antioxidant, or may comprise two or more
kinds. When comprising two or more of them, it is preferable that a
total amount is within the above-mentioned range.
<Mold-Releasing Agent>
[0099] The resin composition of the present invention may comprise
a mold-releasing agent. The mold-releasing agent is preferably at
least one compound selected from an aliphatic carboxylic acid, an
aliphatic carboxylic acid ester, and an aliphatic hydrocarbon
compound having a number-average-molecular weight of 200 to 15000.
Among them, at least one compound selected from the aliphatic
carboxylic acid and the aliphatic carboxylic acid ester is more
preferably used.
[0100] Specific examples of the aliphatic carboxylic acids include
a saturated or unsaturated aliphatic mono-carboxylic acid,
di-carboxylic acid or tri-carboxylic acid. In the present
description, the term of the aliphatic carboxylic acid is used to
encompass an alicyclic carboxylic acid. Among the aliphatic
carboxylic acids, preferable is a mono- or di-carboxylic acid
having 6 to 36 carbon atoms, more preferable is aliphatic saturated
mono-carboxylic acid having 6 to 36 carbon atoms. Specific examples
of such aliphatic carboxylic acids include palmitic acid, stearic
acid, valeric acid, caproic acid, capric acid, lauric acid, arachic
acid, behenic acid, lignoceric acid, cerotic acid, melissic acid,
tetratriacontanoic acid, montanoic acid, glutaric acid, adipic
acid, azelaic acid and the like.
[0101] As an aliphatic carboxylic acid component constituting the
aliphatic carboxylic acid ester, there can be used the same
aliphatic carboxylic acid as mentioned above. In contrast, as an
alcohol component constituting the aliphatic carboxylic acid ester,
there can be used a saturated or unsaturated mono-alcohol, a
saturated or unsaturated polyhydric alcohol and the like. These
alcohols may have a substituent such as a fluorine atom or an aryl
group. Among these alcohols, preferable is a saturated mono- or
polyhydric alcohol having 30 or less carbon atoms, and more
preferable is a saturated aliphatic mono-alcohol or
polyhydric-alcohol having 30 or less carbon atoms. Here, the
aliphatic alcohol also includes an alicyclic alcohol. Specific
examples of the alcohols include octanol, decanol, dodecanol,
stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene
glycol, glycerin, pentaerythritol, 2,2-dihydroxy-perfluoropropanol,
neopentylene glycol, ditrimethylolpropane, dipentaerythritol and
the like. These aliphatic carboxylic acid esters may contain an
aliphatic carboxylic acid and/or alcohol as a contaminant, and may
be a mixture of a plurality of compounds. Specific examples of the
aliphatic carboxylic acid esters include beeswax (mixture
containing myricyl palmitate as a main component), stearyl
stearate, behenyl behenate, octyldodecyl behenate, glycerin
monopalmitate, glycerin monostearate, glycerin distearate, glycerin
tristearate, pentaerythritol monopalmitate, pentaerythritol
monostearate, pentaerythritol distearate, pentaerythritol
tristearate, pentaerythritol tetrastearate and the like.
[0102] When the resin composition of the present invention
comprises the mold-releasing agent, a blending amount of the
mold-releasing agent is 0.01 to 5 parts by weight, and more
preferably 0.05 to 3 parts by weight relative to 100 parts by
weight of the resin component.
[0103] The resin composition of the present invention may comprise
only one kind of the mold-releasing agent, or may comprise two or
more kinds. When comprising two or more of them, it is preferable
that a total amount is within the above-mentioned range.
[0104] The resin composition of the present invention may comprise
other components within the scope not departing from the gist of
the present invention. Examples of the other components include
stabilizers other than the phosphorus-based stabilizer, ultraviolet
absorbents, flame retardants, glass filler and inorganic filler
other than talc, fluorescent whiteners, antidripping agents,
antistatic agents, anticlouding agents, lubricants, antiblocking
agents, flowability-improving agents, plasticizers, dispersing
agents, antibacterial agents and the like. Two or more of these may
be used together.
[0105] As to these components, the description of, for example,
JP-A-2007-314766, JP-A-2008-127485, JP-A-2009-51989, and
JP-A-2012-72338 and the like can be referred to, which are
incorporated herein.
[0106] The method for preparing the polycarbonate resin composition
of the present invention is not particularly defined, and known
preparation methods of thermoplastic resin composition can be
employed widely. Specifically, the resin composition can be
prepared by previously mixing each component through the use of
various mixers such as tumbler mixer, Henschel mixer, and then
melt-molding with Banbury mixer, roll, Brabender, uniaxial kneading
extruder, twin screw kneading extruder, kneader and the like.
[0107] Alternatively, for example, the resin composition of the
present invention can be prepared by supplying through a feeder to
an extruder without pre-mixing of each component or with pre-mixing
of partial components, and melt-kneading. Furthermore, for example,
the resin composition of the present invention can also be prepared
by pre-mixing a part of the components, supplying it to an
extruder, performing melt-kneading to thereby obtain a resin
composition that is set as a master batch, mixing again the master
batch with the remaining components, and then performing
melt-kneading.
[0108] The method for manufacturing the resin-molded article from
the resin composition of the present invention is not particularly
limited, and there can be employed molding method generally used in
thermoplastic resins such as, namely, usual injection molding,
super high speed injection molding, injection compression molding,
two color molding, blow molding including gas-assist, molding by
using a heat insulating die, molding by using a rapid heating die,
foam molding (including supercritical fluid), insert molding, IMC
(in-mold coating molding) molding, extrusion molding, sheet
molding, heat molding, rotation molding, laminate molding, and
press molding. In addition, there can be selected a molding method
using hot-runner system.
[0109] Next, a process of providing a plated layer on the surface
of the resin-molded article obtained by molding the resin
composition of the present invention will be explained according to
FIG. 1. FIG. 1 shows a schematic view of a process of forming a
plated layer on a surface of a resin-molded article 1 by laser
direct structuring technique. In FIG. 1, although the resin-molded
article 1 is a flat substrate, the resin-molded article is not
necessarily such a flat substrate, and may be partially or totally
curved. The resin-molded article comprises not only final products
but also various parts. The resin-molded article of the present
invention is preferably a mobile electronic device part. The mobile
electronic device parts have high impact resistance and rigidity
together with excellent heat resistance, and have features of low
anisotropy and low warpage, and thus, are extremely suitable for
inside components and casing of PDA such as electronic organizer or
portable computer; beeper; cellular phone; PHS; and the like.
Particularly suitable is a flat plate-like mobile electronic device
part having an average thickness excluding rib of 1.2 mm or less
(lower limit is not particularly defined and, for example 0.4 mm or
more), and among them, most suitable is the casing.
[0110] Returning to FIG. 1 again, the resin-molded article 1 is
irradiated with laser 2. The laser herein is not particularly
defined, and can be appropriately selected from known lasers such
as YAG laser, excimer laser, electromagnetic radiations, and
preferable is YAG laser. Moreover, a wavelength of the laser is not
particularly defined. Preferred wavelength range is 200 nm to 1200
nm. Particularly preferable is 800 nm to 1200 nm.
[0111] When irradiated with laser, the resin-molded article 1 is
activated at only the portion 3 irradiated with the laser. Under
this activated condition, the resin-molded article 1 is applied to
a plating solution 4. The plating solution 4 is not particularly
defined, and known plating solutions can be employed widely, and,
as a metal component, a component in which copper, nickel, gold,
silver, or palladium is mixed is preferable, and a component in
which copper is mixed is more preferable.
[0112] The method for applying the resin-molded article 1 to the
plating solution 4 is not particularly defined, and, for example,
there is a method for throwing the resin-molded article 1 into a
liquid with which the plating solution 4 is blended. With respect
to the resin-molded article after applying the plating solution, a
plated layer 5 is formed only on the portion irradiated with the
laser.
[0113] According to the method of the present invention, circuit
lines having an interval width of 1 mm or less, further 150 .mu.m
or less (lower limit is not particularly defined and is, for
example, 30 .mu.m or more) can be formed. Such a circuit is
preferably used as an antenna of mobile electronic device parts.
Namely, one preferred embodiment of the resin-molded article of the
present invention is a resin-molded article in which a plated layer
provided on the surface of mobile electronic device parts has
performance as an antenna.
EXAMPLE
[0114] Hereinafter, the present invention will be more specifically
explained by referring to Examples. Materials, amounts to be used,
proportions, contents of treatment, procedures for treatment and
the like described in the following Examples can be appropriately
changed within a scope not departing the gist of the present
invention. Accordingly, the scope of the present invention is not
limited by the following specific examples.
<Resin Component>
[0115] S-3000F: Polycarbonate resin manufactured by Mitsubishi
Engineering-Plastics Corporation AT-08: ABS resin manufactured by
NIPPON A&L Inc.
<Glass Filler>
[0116] MF-S-R: Milled fiber with an average fiber diameter of 10
.mu.m, an average fiber length of 110 .mu.m, surface-treated with a
phosphorous acid, manufactured by ASAHI FIBER GLASS Co., Ltd.
MF06-JB1: Milled fiber with an average fiber diameter of 10 .mu.m,
an average fiber length of 70 .mu.m, no surface-treated,
manufactured by ASAHI FIBER GLASS Co., Ltd. PFE301S: Milled fiber
with an average fiber diameter of 10 .mu.m, an average fiber length
of 30 .mu.m, surface-treated with acrylsilane, manufactured by
Nitto Boseki Co., Ltd. T-571: Chopped strand with 13 .mu.m
diameter, and use of an urethane resin as a sizing agent,
manufactured by Nippon Electric Glass Co., Ltd.
<LDS Additive>
[0117] CP5C: manufactured by Keeling & Walker antimony-doped
tin oxide (tin oxide 95% by weight, antimony oxide 5% by weight,
lead oxide 0.02% by weight, copper oxide 0.004% by weight) W-1:
manufactured by Mitsubishi Materials Corporation antimony-doped tin
oxide coted titanium oxide (titanium oxide 79% by weight, tin oxide
18% by weight, antimony oxide 3% by weight) STOX-M: manufactured by
NIHON SEIKO CO., LTD, mixture of antimony trioxide (antimony oxide
99.1% by weight, organosiloxane 0.5% by weight, lead oxide 0.05% by
weight, cyan oxide 0.05% by weight) T-1: manufactured by Mitsubishi
Materials Corporation, antimony-doped tin oxide (tin oxide 90.1% by
weight, antimony oxide 9.9% by weight)
<Talc>
5000S: Hayashi-kasei co., jp
<Elastomer>
[0118] KANEACE M-711: Core/shell type elastomer including
butadiene-based core and acrylic shell manufactured by KANEKA
CORPORATION
<White Pigment>
[0119] Titanium oxide treated with methylhydrogenesiloxane
manufactured by RESINO COLOR INDUSTRIES CO., LTD.,
<Phosphorus-Based Stabilizer>
ADEKA Stub PEP-36:
[0120] Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol
diphosphite manufactured by ADEKA CORPORATION ADEKA Stub AX71:
Mixture of approximately equal mole of (mono- and di-stearic acid
phosphate) manufactured by ADEKA CORPORATION ADEKA Stub PEP-8:
(Cyclic neopentanetetrayl bis(octadecyl phosphite)) manufactured by
ADEKA CORPORATION ADEKA Stub ADK2112:
Tris(2,4-di-tert-butylphenyl)phosphite manufactured by ADEKA
CORPORATION
<Antioxidant>
Irganox 1076:
[0121] Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate
manufactured by BASF
<Mold-Releasing Agent>
[0122] VPG861: Pentaerythritol tetrastearate manufactured by Cognis
Oleo Chemicals Japan
<Compound>
[0123] After weighting each component according to the formulations
mentioned in the following Tables, and mixing with a tumbler for 20
minutes, the mixture was supplied to (TEX30HSST) with one bent
manufactured by The Japan Steel Works, LTD., to knead under the
conditions of a screw rotational speed of 200 rpm, discharge of 20
kg/hr, a barrel temperature of 300.degree. C., and the molten resin
extruded in the form of strand was cooled rapidly in a water tank,
and then pelletized by using a pelletizer to obtain pellets of the
resin composition.
<Preparation of Test Piece-ISO Dumbbell Test Piece>
[0124] After drying, at 120.degree. C. for 5 hours, the pellets
obtained by the above-mentioned preparation method,
injection-molding was performed for the formation of ISO dumbbell
test pieces having 4 mmt and 3 mmt, under the conditions of a
cylinder temperature of 300.degree. C., a die temperature of
100.degree. C., a molding cycle of 50 seconds through the use of
SG75-MII manufactured by Nissei Plastic Industrial Co., Ltd.
<Preparation of Test Piece--Two-Stage Plate of 2 mmt/3
mmt>
[0125] After drying, at 120.degree. C. for 5 hours, the pellets
obtained by the above-mentioned preparation method,
injection-molding was performed for the formation of a two-stage
plate of 2 mmt/3 mmt, under the conditions of a cylinder
temperature of 300.degree. C., a die temperature of 100.degree. C.,
a molding cycle of 30 seconds through the use of J-50 manufactured
by Nissei Plastic Industrial Co., Ltd.
<Charpy Impact Strength>
[0126] In accordance with ISO179, through the use of the ISO
dumbbell test piece having 3 mmt obtained by the above-mentioned
method, a charpy impact strength with notches was measured under
23.degree. C. The results are shown in the following Tables.
<Plating Property (LDS Activity)--Plating Index>
[0127] The laser irradiation of the surface of the two-stage plate
of 2 mmt/3 mmt was performed by using YAG laser having a wavelength
of 1064 nm under the condition of output power of 10 W, frequency
of 80 kHz and rate of 3 m/s, and then the surface was subjected to
electroless plating in a plating bath of M-Copper85 manufactured by
MacDermid Co., Ltd. The LDS activity was evaluated depending on a
thickness of the copper plaited layer, when the thickness of an
electroless plating of the standard material is 1.0.
<Dielectric Constant and Dielectric Tangent>
[0128] A molded article of 100 mm square, 1 mm thickness was
prepared through the use of an injection molding machine NEX80
manufactured by Nissei Plastic Industrial Co., Ltd. through a fine
gate die. Test pieces of 1 mm.times.1 mm.times.100 mm were produced
from the molded article in the flowing direction of resin
(parallel) and in the direction perpendicular to the flowing
direction of resin (perpendicularity).
[0129] These test pieces were subjected to measurement of
dielectric constant and dielectric tangent at 2.45 GHz through the
use of a cylindrical cavity resonator manufactured by Kanto
Electric Application and Development Inc.
<Hue-Gray Lightness>
[0130] Through the use of a gray scale no-gloss plate manufactured
by Mansell, lightness was measured by using a scale of W (white) to
BK (black). Gray lightness was shown as the index of white.
<Decomposition-MVR>
[0131] After drying the resin composition pellets obtained above at
100.degree. C. for 4 to 8 hours, a melt volume rate (MVR) was
measured through the use of MELT INDEXER RF-F01 manufactured by
TOYO SEIKI KOGYO CO., LTD. under a measuring temperature of
270.degree. C., a load of 5 kgf. It can be said that the higher the
MVR value is, the more the decomposition proceeds.
<Decomposition-Post Heat-Aging MVR>
[0132] After storing the resin composition pellets obtained above
at 100.degree. C. for one week, a melt volume rate (MVR) was
measured through the use of MELTINDEXERF-F01 manufactured by TOYO
SEIKI KOGYO CO., LTD. under a measuring temperature of 270.degree.
C., a load of 5 kgf. It can be said that the higher the MVR value
is, the more the decomposition proceeds.
<Decomposition-Moist-Heat Test MVR>
[0133] After storing the resin composition pellets obtained above
under the circumstance of 80.degree. C., 95% relative humidity (RH)
for one week, a melt volume rate (MVR) was measured through the use
of MELTINDEXERF-F01 manufactured by TOYO SEIKI KOGYO CO., LTD.
under a measuring temperature of 270.degree. C., a load of 5 kgf.
It can be said that the higher the MVR value is, the more the
decomposition proceeds.
[0134] The results are shown in the following Tables. In the
Tables, the blending amount is represented by parts by weight.
TABLE-US-00001 TABLE 1 Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Ex- Kind
Name ample 1 ample 2 ample 3 ample 4 ample 5 ample 6 ample 7 ample
8 ample 9 ample 10 PC S-3000F 100 100 100 60 60 60 60 60 60 60 ABS
AT-08 40 40 40 40 40 40 40 Glass filler MF-S-R 11 25 43 11 25 43 43
43 MF06-JB1 43 PFE301S 43 T-571 LDS CP5C 4 4 4 4 4 4 4 4 4 8
additive W-1 STOX-M T-1 Talc 5000s 5 Elastomer M711 5 5 5 5 5 5 5 5
5 5 White Titanium oxide 3 3 3 3 3 3 3 3 3 3 Pigment treated with
methylhydro- genesiloxane Phosphorus- PEP-36 0.05 0.05 0.05 0.05
0.05 0.05 0.05 0.05 0.05 0.05 based AX71 stabilizer PEP-8 ADK2112
Antioxidant Irganox1076 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Mold- VPG861 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 releasing
agent Mechanical Charpy impact 10 13 15 9 11 12 12 11 7 13 property
strength Plating Plating Index 0.6 0.65 0.7 0.7 0.75 0.8 0.8 0.85
0.9 0.9 property Dielectric Paralell 2.8 2.98 3.16 2.78 2.96 3.14
3.14 3.14 3.16 3.26 constant Perpendi- 2.8 2.98 3.16 2.78 2.96 3.14
3.14 3.14 3.16 3.26 2.45 GHz cularity Dielectric Paralell 0.006
0.007 0.008 0.006 0.007 0.008 0.008 0.008 0.008 0.009 tangent
perpendi- 0.006 0.007 0.008 0.006 0.007 0.008 0.008 0.008 0.008
0.009 2.45 GHz cularity Hue Gray lightness 8 8 8 8 8 8 8 8 8 7.5
Decom- MVR 16 14 12 25 22 18 20 22 22 22 position Post heat-aging
18 16 14 27 24 20 22 24 25 24 MVR Moist-heat test 19 17 15 28 25 21
26 25 28 25 MVR
TABLE-US-00002 TABLE 2 Ex- Ex- Ex- Ex- Ex- Comp. Comp. Comp. Comp.
Kind Name ample 11 ample 12 ample 13 ample 14 ample 15 Example 1
Example 2 Example 3 Example 4 PC S-3000F 60 60 60 60 60 100 100 60
60 ABS AT-08 40 40 40 40 40 40 40 Glass filler MF-S-R 43 43 43 43
43 MF06-JB1 PFE301S T-571 25 25 25 25 LDS additive CP5C 4 4 4 4 4
W-1 STOX-M 4 4 T-1 4 4 Talc 5000s Elastomer M711 5 5 5 5 5 5 5 5 5
White Pigment Titanium oxide 3 3 3 3 3 3 3 3 3 treated with methyl-
hydrogenesiloxane Phosphorus-based PEP-36 0.05 0.05 0.05 0.05
stabilizer AX71 0.05 PEP-8 0.05 ADK2112 0.05 Antioxidant
Irganox1076 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Mold-releasing agent
VPG861 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Mechanical property
Charpy impact 11 12 12 12 12 10 10 8 8 strength Plating property
Plating Index 0.8 0.8 0.8 0.8 0.8 0.8 0.1 0.1 0.1 Dielectric
constant Paralell 3.14 3.14 3.14 3.14 3.14 3.5 3.03 3.5 3.03 2.45
GHz Perpendicularity 3.14 3.14 3.14 3.14 3.14 3.36 2.89 3.36 2.89
Dielectric tangent Paralell 0.008 0.008 0.008 0.008 0.008 0.011
0.008 0.011 0.008 2.45 GHz perpendicularity 0.008 0.008 0.008 0.008
0.008 0.011 0.008 0.011 0.008 Hue Gray lightness 8 8 8 8 8 5 4 5 4
Decomposition MVR 18 18 22 22 20 15 15 23 24 Post heat-aging 19 20
35 33 30 17 17 25 25 MVR Moist-heat test 20 22 40 40 35 18 18 26 26
MVR
TABLE-US-00003 TABLE 3 Kind Name Example 16 Example 17 Example 18
Example 19 Example 20 Example 21 Example 22 PC S-3000F 100 100 100
60 60 60 60 ABS AT-08 40 40 40 40 Glass filler MF-S-R 11 25 43 11
25 43 MF06-JB1 43 PFE301S T-571 LDS additive CP5C W-1 4 4 4 4 4 4 4
STOX-M T-1 Talc 5000s Elastomer M711 5 5 5 5 5 5 5 White Pigment
Titanium oxide 2 2 2 2 2 2 2 treated with methylhydro- genesiloxane
Phosphorus- PEP-36 0.05 0.05 0.05 0.05 0.05 0.05 0.05 based AX71
stabilizer PEP-8 ADK2112 Antioxidant Irganox1076 0.1 0.1 0.1 0.1
0.1 0.1 0.1 Mold- VPG861 0.3 0.3 0.3 0.3 0.3 0.3 0.3 releasing
agent Mechanical Charpy impact 10 13 15 9 11 12 12 property
strength Plating Plating Index 0.5 0.55 0.6 0.6 0.65 0.7 0.7
property Dielectric con- Paralell 2.8 2.98 3.16 2.78 2.96 3.14 3.14
stant 2.45 GHz Perpendicularity 2.8 2.98 3.16 2.78 2.96 3.14 3.14
Dielectric tan- Paralell 0.006 0.007 0.008 0.006 0.007 0.008 0.008
gent 2.45 GHz perpendicularity 0.006 0.007 0.008 0.006 0.007 0.008
0.008 Hue Gray lightness 8 8 8 8 8 8 8 Decom- MVR 16 14 12 25 22 18
20 position Post heat-aging 18 16 14 27 24 20 22 MVR Moist-heat
test 19 17 15 28 25 21 23 MVR
TABLE-US-00004 TABLE 4 Kind Name Example 23 Example 24 Example 25
Example 26 Example 27 Example 28 Example 29 Example 30 PC S-3000F
60 60 60 60 60 60 60 60 ABS AT-08 40 40 40 40 40 40 40 40 Glass
filler MF-S-R 43 43 43 43 43 43 43 MF06-JB1 PFE301S 43 T-571 LDS
additive CP5C W-1 4 4 8 4 4 4 4 4 STOX-M T-1 Talc 5000s 5 Elastomer
M711 5 5 5 5 5 5 5 5 White Pigment Titanium oxide 2 2 2 2 2 2 2 2
treated with methylhydro- genesiloxane Phosphorus- PEP-36 0.05 0.05
0.05 based stabilizer AX71 0.05 PEP-8 0.05 ADK2112 0.05 Antioxidant
Irganox1076 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Mold-releasing VPG861 0.3
0.3 0.3 0.3 0.3 0.3 0.3 0.3 agent Mechanical Charpy impact 11 7 13
11 12 12 12 12 property strength Plating property Plating Index
0.75 0.8 0.8 0.7 0.7 0.7 0.7 0.7 Dielectric Paralell 3.14 3.16 3.26
3.14 3.14 3.14 3.14 3.14 constant 2.45 GHz Perpendicularity 3.14
3.16 3.26 3.14 3.14 3.14 3.14 3.14 Dielectric Paralell 0.008 0.008
0.009 0.008 0.008 0.008 0.008 0.008 tangent 2.45 GHz
perpendicularity 0.008 0.008 0.009 0.008 0.008 0.008 0.008 0.008
Hue Gray lightness 8 8 7.5 8 8 8 8 8 Decomposition MVR 22 23 23 18
18 20 20 19 Post heat-aging 23 25 25 19 20 30 28 25 MVR Moist-heat
test 24 29 30 20 22 35 35 33 MVR
[0135] As is clear from the above Tables, it has been found that
the resin composition of the present invention is excellent in
plating property. In contrast, the compositions of Comparative
Examples were not able to exhibit sufficient plating property.
Furthermore, it has been found that the resin composition of the
present invention is excellent in mechanical properties, excellent
in hue, and is hard to be decomposed. That is, according to the
resin composition of the present invention, it has been found that
the plating property can be enhanced with maintaining various
performances.
[0136] The present disclosure relates to the subject matter
contained in Japanese Patent Application No. 203364/2012 filed on
Sep. 14, 2012, which is expressly incorporated herein by reference
in their entirety. All the publications referred to in the present
specification are also expressly incorporated herein by reference
in their entirety.
[0137] The foregoing description of preferred embodiments of the
invention has been presented for purposes of illustration and
description, and is not intended to be exhaustive or to limit the
invention to the precise form disclosed. The description was
selected to best explain the principles of the invention and their
practical application to enable others skilled in the art to best
utilize the invention in various embodiments and various
modifications as are suited to the particular use contemplated. It
is intended that the scope of the invention not be limited by the
specification, but be defined claims set forth below.
* * * * *